US20190185970A1 - HOT-DIP Al-Zn ALLOY COATED STEEL SHEET - Google Patents

HOT-DIP Al-Zn ALLOY COATED STEEL SHEET Download PDF

Info

Publication number
US20190185970A1
US20190185970A1 US16/330,158 US201716330158A US2019185970A1 US 20190185970 A1 US20190185970 A1 US 20190185970A1 US 201716330158 A US201716330158 A US 201716330158A US 2019185970 A1 US2019185970 A1 US 2019185970A1
Authority
US
United States
Prior art keywords
hot
dip
steel sheet
coated steel
alloy coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US16/330,158
Inventor
Masahiro Yoshida
Akira Matsuzaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
Original Assignee
JFE Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JFE Steel Corp filed Critical JFE Steel Corp
Assigned to JFE STEEL CORPORATION reassignment JFE STEEL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MATSUZAKI, AKIRA, YOSHIDA, MASAHIRO
Publication of US20190185970A1 publication Critical patent/US20190185970A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/10Alloys based on aluminium with zinc as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/012Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • C22C18/04Alloys based on zinc with aluminium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12Aluminium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36Elongated material
    • C23C2/40Plates; Strips

Definitions

  • This disclosure relates to a hot-dip Al—Zn alloy coated steel sheet with excellent corrosion resistance after coating.
  • a hot-dip Al—Zn alloy coated steel sheet such as a hot-dip Al—Zn alloy coated steel sheet containing 25 mass % to 90 mass % of Al in the zinc or zinc alloy coating layer, shows better corrosion resistance than a hot-dip galvanized steel sheet.
  • the hot-dip Al—Zn alloy coated steel sheet is produced by using a thin steel sheet, which is obtained by hot rolling or cold rolling a slab, as the base steel sheet, and subjecting the base steel sheet to recrystallization annealing and hot-dip coating treatment in an annealing furnace of a continuous galvanizing line (CGL).
  • the hot-dip Al—Zn alloy coating layer thus formed has an alloy phase existing in the interface with the base steel sheet, and an upper layer existing thereon.
  • the upper layer is mainly composed of a dendrite solidification part where Al is solidified by dendrite solidification and Zn is contained in a supersaturated state ( ⁇ -Al phase), and a remaining interdendritic part (Zn rich phase).
  • the dendrite solidification part is laminated in the thickness direction of the hot-dip coating layer. Because of the characteristic coating structure of the upper layer, the course of corrosion development from surfaces becomes complicated and the corrosion is less likely to reach the base steel sheet. In this way, the hot-dip Al—Zn alloy coated steel sheet obtains better corrosion resistance than a hot-dip galvanized steel sheet whose hot-dip coating layer has the same thickness.
  • the molten bath normally contains inevitable impurities and Fe eluted from, for example, steel sheets and equipment in the molten bath, and is further added with Si to inhibit excessive growth of the alloy phase.
  • Si exists in the alloy phase in the form of intermetallic compound, or exists in the upper layer in the form of intermetallic compound, solid solution, or simple substance.
  • Si provides an effect of inhibiting the growth of the alloy phase in the interface of the hot-dip Al—Zn alloy coated steel sheet, so that the thickness of the alloy phase is around 1 ⁇ m to 5 ⁇ m.
  • the thickness of the hot-dip coating layer is the same, the thinner the alloy phase is, the thicker the upper layer, which has an effect of improving corrosion resistance, is.
  • inhibiting the growth of the alloy phase contributes to the improvement of corrosion resistance.
  • the alloy phase is harder than the upper layer and acts as the origin of cracks during processing. Therefore, inhibiting the growth of the alloy phase also provides an effect of reducing crack generation and improving bending workability.
  • the base steel sheet is exposed and the corrosion resistance is deteriorated. Therefore, inhibiting the growth of the alloy phase and inhibiting the generation of cracks improves the corrosion resistance of bending parts.
  • hot-dip Al—Zn alloy coated steel sheets with excellent corrosion resistance is increasing mainly in the field of building materials such as roofs and walls which will be exposed to outdoors for a long time.
  • the hot-dip Al—Zn alloy coated steel sheets have also been used in the field of automobiles. Particularly in the field of automobiles, it is required, as one of the countermeasures against global warming, to reduce the weight of an automotive body to improve fuel efficiency and reduce CO 2 emissions. For this reason, weight reduction achieved by using high strength steel sheets, and gauge reduction achieved by improving the corrosion resistance of steel sheets are strongly desired.
  • using hot-dip Al—Zn alloy coated steel sheets in the field of automobiles, particularly for outer panels has the following problems.
  • the hot-dip coated steel sheets are delivered to, for example, automobile manufacturers in a state where hot-dip coating has already been applied on the steel sheets by a continuous galvanizing line (CGL), subsequently the steel sheets are worked into shapes of panel components, and then subjected to chemical conversion treatment and three-coat refinishing for automobiles consisting of electrodeposition coating, intercoating, and top coating.
  • CGL continuous galvanizing line
  • the hot-dip coated steel sheets are hot-dip Al—Zn alloy coated steel sheets
  • selective corrosion of the Zn rich phase occurs in the interface between the coating film and the hot-dip coating with the edge surfaces of the steel sheets acting as the origin, as in the case of automobile outer panels.
  • edge creeps significantly larger than when using hot-dip Zn alloy coating were caused and corrosion resistance after coating was deteriorated.
  • PTL 1 JP 2002 012959 A describes a hot-dip Al—Zn alloy coated steel sheet, where Mg, and further, for example, Sn are added to the coating composition, to form Mg compounds such as Mg 2 Si, MgZn 2 , Mg 2 Sn in the hot-dip coating layer to inhibit generation of red rust from the edge surfaces of the steel sheet.
  • PTL 2 (WO 2007 108496 A) describes a hot-dip Al—Zn alloy coated steel sheet with both high corrosion resistance and high workability, where the hot-dip coating layer contains, by mass %, 35% or more of Zn, 1% to 60% of Mg, 0.07% to 59% of Al, and at least one of 0.1% to 10% of La, 0.1% to 10% of Ce, 0.1% to 10% of Ca, 0.1% to 10% of Sn, 0.005% to 2% of P and 0.02% to 7% of Si.
  • a hot-dip Al—Zn alloy coated steel sheet comprising a base steel sheet and a hot-dip coating layer formed on a surface of the base steel sheet, wherein the hot-dip coating layer contains, by mass %, Al: 25% to 80% and Ce: 0.1% to 3%, the balance being Zn and inevitable impurities.
  • thermoforming a hot-dip Al—Zn alloy coated steel sheet with excellent corrosion resistance after coating By making the presently disclosed hot-dip Al—Zn alloy coated steel sheet into a high strength steel sheet, it is possible to achieve both weight reduction and excellent corrosion resistance in the field of automobiles. Furthermore, by using the presently disclosed hot-dip Al—Zn alloy coated steel sheet in the field of building materials as roof materials or wall materials, it is possible to prolong the life of buildings.
  • FIG. 1 illustrates a sample for evaluating corrosion resistance after coating
  • FIG. 2 illustrates the cycle of the corrosion acceleration test.
  • the presently disclosed hot-dip Al—Zn alloy coated steel sheet contains Al and 0.1% to 3% of Ce in the hot-dip coating layer. Containing Ce in the hot-dip coating layer can improve corrosion resistance after coating, which is the problem of the present disclosure.
  • the Ce content in the hot-dip coating layer is 0.1% or more.
  • the Ce content is preferably 0.5% or more from the perspective of further improving corrosion resistance after coating.
  • the Ce content in the hot-dip coating layer exceeds 3%, not only is the effect saturated, but also the corrosion of the Ce compounds occurs severely and the solubility of the entire hot-dip coating layer increases excessively. As a result, the dissolution rate is high even if the corrosion products are stabilized, and this leads to a large blister width and deterioration in corrosion resistance after coating. Therefore, the Ce content in the hot-dip coating layer is 3% or less.
  • the Ce content is preferably 2% or less from the perspective of further improving corrosion resistance after coating.
  • the presently disclosed hot-dip Al—Zn alloy coated steel sheet is a hot-dip Al—Zn alloy coated steel sheet containing 25% to 80% of Al in the hot-dip coating layer.
  • the Al content in the hot-dip coating layer is preferably 45% or more and more preferably 50% or more from the perspective of balancing corrosion resistance with actual operation requirements.
  • the Al content in the hot-dip coating layer is preferably 70% or less and more preferably 60% or less from the same perspective of balancing corrosion resistance with actual operation requirements.
  • the aforementioned dendrite solidification of Al occurs in the upper layer existing on the alloy layer existing in the interface with the base steel sheet.
  • the upper layer is mainly composed of a part where Zn is contained in a supersaturated state and Al is solidified by dendrite solidification, and a remaining interdendritic part, and has a structure with excellent corrosion resistance where the dendrite solidification part is laminated in the thickness direction of the hot-dip coating layer.
  • the Al content is preferably 45% or more in order to stably obtain such a hot-dip coating phase structure.
  • the Al content is preferably 70% or less in order to obtain sufficient corrosion resistance even with a small coating weight.
  • the molten bath temperature (hereinafter referred to as “bath temperature”) rises as the Al content increases, and this may lead to actual operation problems.
  • the bath temperature would be appropriate and no problem would be caused with the aforementioned Al content.
  • the base steel sheet used for the presently disclosed hot-dip Al—Zn alloy coated steel sheet is not limited to a particular type.
  • a hot rolled steel sheet or steel strip which has been subjected to acid pickling descaling, or a cold rolled steel sheet or steel strip obtained by cold rolling the hot rolled steel sheet or steel strip may be used.
  • the presently disclosed hot-dip coated steel sheet contains Zn as the balance in the hot-dip coating layer.
  • the content of Zn is not particularly limited and can be appropriately changed according to the contents of other components. However, it is preferably 10% or more. When the Zn content is 10% or more, the hot-dip coating provides a sufficient sacrificial protection effect against Fe, so that better corrosion resistance can be obtained when the steel base is exposed.
  • the presently disclosed hot-dip coated steel sheet preferably contains 0.1% to 10% of Si in the hot-dip coating layer.
  • Si is added in the molten bath to inhibit the growth of the interfacial alloy phase formed in the interface with the base steel sheet and to improve corrosion resistance and workability. Therefore, Si is contained in the hot-dip coating layer.
  • an alloying reaction between Fe in the steel sheet surface and Al or Si in the bath takes place as soon as the steel sheet is immersed in the molten bath, to form Fe—Al based and/or Fe—Al—Si based compounds.
  • the formation of Fe—Al—Si based compound inhibits the growth of the interfacial alloy phase.
  • the Si content is more preferably 1.0% or more in order to sufficiently obtain the growth inhibiting effect.
  • the Si content in the molten bath is preferably 10% or less.
  • the preferable range of the Si content in the molten bath is 0.1% to 10%.
  • the composition of the hot-dip coating layer of the produced Al—Zn alloy coated steel sheet is substantially the same as the composition of the molten bath. Therefore, the range of the Si content in the hot-dip coating layer is preferably the same as the preferable range of the Si content in the molten bath i.e. a range of 0.1% to 10%.
  • the hot-dip coating layer preferably contains at least one element selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr, and B in a total amount of 0.01% to 10%. This is because these elements provide an effect of improving the stability of corrosion products and delaying the progressing of corrosion.
  • the chemical composition of the hot-dip coating layer can be verified by, for example, immersing and dissolving the hot-dip coating layer in, for example, hydrochloric acid, and performing ICP emission spectral analysis or atomic absorption analysis on the solution.
  • This method is intended to be an example rather than a limitation. Any method may be used as long as it can precisely quantify the chemical composition of the hot-dip coating layer.
  • the components other than the aforementioned chemical composition of the hot-dip coating layer are inevitable impurities. This means that it is within the scope of the present disclosure to include inevitable impurities and other trace element unless existence thereof adversely affects the operation and effect of the present disclosure.
  • the hot-dip coating layer contains no Mg. In this way, it is possible to inhibit the occurrence of dross resulting from the oxidation of Mg, which is an oxidizable element, thereby inhibiting the occurrence of surface defects caused by the dross.
  • the presently disclosed hot-dip Al—Zn alloy coated steel sheet can be produced by, for example, galvanizing facilities such as a continuous galvanizing line, and conventional methods may be used except for the composition management of the molten bath.
  • the composition of the molten bath includes 25 mass % to 80 mass % of Al and 0.1% to 3% of Ce, with the balance being Zn and inevitable impurities.
  • a molten bath of such a composition it is possible to produce the presently disclosed hot-dip Al—Zn alloy coated steel sheet with the aforementioned hot-dip coating layer structure.
  • any element other than the aforementioned Al, Zn, Si and Ce in the molten bath as long as the effect of the present disclosure is not impaired.
  • Each sample hot-dip Al—Zn alloy coated steel sheet was produced by a continuous galvanizing line (CGL) using a cold rolled steel sheet with a sheet thickness of 0.8 mm produced by a conventional method as the base steel sheet, where the bath temperature of the molten bath was as listed in Table 1, and the coating weight was 50 g/m 2 per side and 100 g/m 2 for both sides.
  • CGL continuous galvanizing line
  • Each sample hot-dip Al—Zn alloy coated steel sheet was punched out to 100 mm in diameter, and immersed in hydrochloric acid to dissolve the hot-dip coating layer. Subsequently, the composition of the dissolving solution was verified by performing quantification based on ICP emission spectral analysis.
  • the composition of the hot-dip coating layer of each sample is listed in Table 1.
  • Each sample hot-dip Al—Zn alloy coated steel sheet was sheared into a size of 90 mm ⁇ 70 mm, and then subjected to zinc phosphate treatment as chemical conversion treatment, followed by electrodeposition coating, intercoating and top coating, which was similar to the coating treatment for automobile outer panels.
  • the zinc phosphate treatment, electrodeposition coating, intercoating and top coating were performed under the following conditions.
  • Chemical conversion treatment was performed using a degreasing agent: FC-E2001, a surface adjusting agent: PL-X, and a chemical conversion treatment agent: PB-AX35M (temperature: 35° C.) manufactured by Nihon Parkerizing Co., Ltd., where the free fluorine concentration of the chemical conversion treatment liquid was 200 mass ppm, and the immersion time of the chemical conversion treatment liquid was 120 seconds.
  • Electrodeposition coating was performed using an electrodeposition coating material: GT-100 manufactured by Kansai Paint Co., Ltd., to obtain a coating thickness of 15 ⁇ m.
  • Spray coating was performed using an intercoating material: TP-65-P manufactured by Kansai Paint Co., Ltd., to obtain a coating thickness of 30 ⁇ m.
  • Spray coating was performed using a top coating material: Neo6000 manufactured by Kansai Paint Co., Ltd., to obtain a coating thickness of 30 ⁇ m.
  • samples for evaluating corrosion resistance after coating were prepared by sealing 5 mm of the end of the surface to be evaluated and the surface not to be evaluated (back surface) with a tape, and then making a cross cut in the center of the surface to be evaluated with a depth reaching the base steel of the hot-dip coated steel sheet, a length of 60 mm and a central angle of 90° by a utility knife, as illustrated in FIG. 1 .
  • a corrosion acceleration test was performed using the samples for evaluation along the cycle illustrated in FIG. 2 .
  • the corrosion acceleration test started from humid atmosphere and was conducted for 60 cycles. Subsequently, the width of the coating film blister which was the largest coating film blister from the damaged part (maximum coating film blister width) was measured, and the corrosion resistance after coating was evaluated based on the following criteria. The evaluation results are listed in Table 1.
  • the samples of the present disclosure were different from the samples of the comparative examples and had a maximum coating film blister width of 1.5 mm or less. Therefore, it is understood that hot-dip Al—Zn alloy coated steel sheets with excellent corrosion resistance after coating were obtained. Furthermore, it is understood from the samples of the present disclosure that, by limiting the Ce content in the hot-dip coating layer of each sample within an appropriate range, hot-dip Al—Zn alloy coated steel sheets with excellent corrosion resistance after coating can be obtained.
  • the presently disclosed hot-dip Al—Zn alloy coated steel sheet has excellent corrosion resistance after coating, and can be applied in a wide range of fields such as automobiles, household electric appliances, and building materials. Particularly in the field of automobiles, when the present disclosure is applied to a high strength steel sheet, it can be used as a surface-treated steel sheet which achieves automobile weight reduction and high corrosion resistance.

Abstract

This disclosure provides a hot-dip Al—Zn alloy coated steel sheet with excellent corrosion resistance after coating. The presently disclosed hot-dip Al—Zn alloy coated steel sheet has a hot-dip coating layer containing, by mass %, Al: 25% to 80% and Ce: 0.1% to 3%, where the balance is Zn and inevitable impurities.

Description

    TECHNICAL FIELD
  • This disclosure relates to a hot-dip Al—Zn alloy coated steel sheet with excellent corrosion resistance after coating.
  • BACKGROUND
  • A hot-dip Al—Zn alloy coated steel sheet, such as a hot-dip Al—Zn alloy coated steel sheet containing 25 mass % to 90 mass % of Al in the zinc or zinc alloy coating layer, shows better corrosion resistance than a hot-dip galvanized steel sheet.
  • Generally, the hot-dip Al—Zn alloy coated steel sheet is produced by using a thin steel sheet, which is obtained by hot rolling or cold rolling a slab, as the base steel sheet, and subjecting the base steel sheet to recrystallization annealing and hot-dip coating treatment in an annealing furnace of a continuous galvanizing line (CGL). The hot-dip Al—Zn alloy coating layer thus formed has an alloy phase existing in the interface with the base steel sheet, and an upper layer existing thereon.
  • Furthermore, the upper layer is mainly composed of a dendrite solidification part where Al is solidified by dendrite solidification and Zn is contained in a supersaturated state (α-Al phase), and a remaining interdendritic part (Zn rich phase). The dendrite solidification part is laminated in the thickness direction of the hot-dip coating layer. Because of the characteristic coating structure of the upper layer, the course of corrosion development from surfaces becomes complicated and the corrosion is less likely to reach the base steel sheet. In this way, the hot-dip Al—Zn alloy coated steel sheet obtains better corrosion resistance than a hot-dip galvanized steel sheet whose hot-dip coating layer has the same thickness.
  • The molten bath normally contains inevitable impurities and Fe eluted from, for example, steel sheets and equipment in the molten bath, and is further added with Si to inhibit excessive growth of the alloy phase. In the molten bath, Si exists in the alloy phase in the form of intermetallic compound, or exists in the upper layer in the form of intermetallic compound, solid solution, or simple substance. Si provides an effect of inhibiting the growth of the alloy phase in the interface of the hot-dip Al—Zn alloy coated steel sheet, so that the thickness of the alloy phase is around 1 μm to 5 μm. When the thickness of the hot-dip coating layer is the same, the thinner the alloy phase is, the thicker the upper layer, which has an effect of improving corrosion resistance, is. Therefore, inhibiting the growth of the alloy phase contributes to the improvement of corrosion resistance. Furthermore, the alloy phase is harder than the upper layer and acts as the origin of cracks during processing. Therefore, inhibiting the growth of the alloy phase also provides an effect of reducing crack generation and improving bending workability. Moreover, in the generated cracks, the base steel sheet is exposed and the corrosion resistance is deteriorated. Therefore, inhibiting the growth of the alloy phase and inhibiting the generation of cracks improves the corrosion resistance of bending parts.
  • A demand for such hot-dip Al—Zn alloy coated steel sheets with excellent corrosion resistance is increasing mainly in the field of building materials such as roofs and walls which will be exposed to outdoors for a long time. Recently, the hot-dip Al—Zn alloy coated steel sheets have also been used in the field of automobiles. Particularly in the field of automobiles, it is required, as one of the countermeasures against global warming, to reduce the weight of an automotive body to improve fuel efficiency and reduce CO2 emissions. For this reason, weight reduction achieved by using high strength steel sheets, and gauge reduction achieved by improving the corrosion resistance of steel sheets are strongly desired. However, using hot-dip Al—Zn alloy coated steel sheets in the field of automobiles, particularly for outer panels, has the following problems.
  • When using hot-dip Al—Zn alloy coated steel sheets as automobile outer panels, generally, the hot-dip coated steel sheets are delivered to, for example, automobile manufacturers in a state where hot-dip coating has already been applied on the steel sheets by a continuous galvanizing line (CGL), subsequently the steel sheets are worked into shapes of panel components, and then subjected to chemical conversion treatment and three-coat refinishing for automobiles consisting of electrodeposition coating, intercoating, and top coating. For outer panels using the hot-dip Al—Zn alloy coated steel sheets, however, if the coating film is damaged, preferential dissolution of Zn (selective corrosion of the Zn rich phase) occurs in the interface between the coating film and the hot-dip coating with the damaged part acting as the origin, due to the characteristic hot-dip coating phase structure consisting of two phases i.e. the aforementioned α-Al phase and Zn rich phase. It progresses deep into the sound part of the coating film and causes a large coating film blister. As a result, there were cases where sufficient corrosion resistance (corrosion resistance after coating) could not be secured.
  • On the other hand, there is also a problem of corrosion resistance after coating when using hot-dip Al—Zn alloy coated steel sheets in the field of building materials as roof materials or wall materials for buildings. When using hot-dip coated steel sheets as roof materials or wall materials, generally, the hot-dip coated steel sheets are delivered to, for example, construction companies in a state where under coating and top coating have already been applied on the steel sheets, subsequently the steel sheets are sheared into a desired size and then subjected to use. For this reason, the edge surfaces of the steel sheets without any coating film are inevitably exposed, and a coating film blister referred to as edge creep may occur with the exposed parts acting as the origin. When the hot-dip coated steel sheets are hot-dip Al—Zn alloy coated steel sheets, selective corrosion of the Zn rich phase occurs in the interface between the coating film and the hot-dip coating with the edge surfaces of the steel sheets acting as the origin, as in the case of automobile outer panels. As a result, there were cases where edge creeps significantly larger than when using hot-dip Zn alloy coating were caused and corrosion resistance after coating was deteriorated.
  • In order to solve the above problems, for example, PTL 1 (JP 2002 012959 A) describes a hot-dip Al—Zn alloy coated steel sheet, where Mg, and further, for example, Sn are added to the coating composition, to form Mg compounds such as Mg2Si, MgZn2, Mg2Sn in the hot-dip coating layer to inhibit generation of red rust from the edge surfaces of the steel sheet.
  • Furthermore, PTL 2 (WO 2007 108496 A) describes a hot-dip Al—Zn alloy coated steel sheet with both high corrosion resistance and high workability, where the hot-dip coating layer contains, by mass %, 35% or more of Zn, 1% to 60% of Mg, 0.07% to 59% of Al, and at least one of 0.1% to 10% of La, 0.1% to 10% of Ce, 0.1% to 10% of Ca, 0.1% to 10% of Sn, 0.005% to 2% of P and 0.02% to 7% of Si.
  • However, even for the hot-dip Al—Zn alloy coated steel sheets described in PTLs 1 and 2 on which a coating film has been applied, the corrosion resistance (corrosion resistance after coating) is still insufficient if the coating film is later damaged. Furthermore, during the production of hot-dip Al—Zn alloy coated steel sheets using an oxidizable element of Mg, more dross are generated and surface defects are more likely to occur than during the production of hot-dip Al—Zn alloy coated steel sheets without Mg, due to the oxidation of Mg. Therefore, a method of improving corrosion resistance without containing Mg has been demanded.
  • CITATION LIST Patent Literature
  • PTL 1: JP 2002 012959 A
  • PTL 2: WO 2007 108496 A
  • SUMMARY Technical Problem
  • It could thus be helpful to provide a hot-dip Al—Zn alloy coated steel sheet with excellent corrosion resistance after coating.
  • Solution to Problem
  • We made intensive studies to solve the aforementioned problems. As a result, we discovered that it is possible to obtain excellent corrosion resistance after coating, which was conventionally considered difficult, by containing Al and a specific amount of Ce in the hot-dip coating layer.
  • This disclosure has been made based on the above discoveries and primary features thereof are as follows.
  • (1) A hot-dip Al—Zn alloy coated steel sheet comprising a base steel sheet and a hot-dip coating layer formed on a surface of the base steel sheet, wherein the hot-dip coating layer contains, by mass %, Al: 25% to 80% and Ce: 0.1% to 3%, the balance being Zn and inevitable impurities.
  • (2) The hot-dip Al—Zn alloy coated steel sheet according to (1), wherein the hot-dip coating layer further contains Si: 0.1 mass % to 10 mass %.
  • (3) The hot-dip Al—Zn alloy coated steel sheet according to (1) or (2), wherein the Al content in the hot-dip coating layer is 45 mass % to 70 mass %.
  • (4) The hot-dip Al—Zn alloy coated steel sheet according to any one of (1) to (3), wherein the Ce content in the hot-dip coating layer is 0.5 mass % to 3 mass %.
  • (5) The hot-dip Al—Zn alloy coated steel sheet according to any one of (1) to (4), wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
  • Advantageous Effect
  • According to this disclosure, it is possible to obtain a hot-dip Al—Zn alloy coated steel sheet with excellent corrosion resistance after coating. By making the presently disclosed hot-dip Al—Zn alloy coated steel sheet into a high strength steel sheet, it is possible to achieve both weight reduction and excellent corrosion resistance in the field of automobiles. Furthermore, by using the presently disclosed hot-dip Al—Zn alloy coated steel sheet in the field of building materials as roof materials or wall materials, it is possible to prolong the life of buildings.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • In the accompanying drawings:
  • FIG. 1 illustrates a sample for evaluating corrosion resistance after coating; and
  • FIG. 2 illustrates the cycle of the corrosion acceleration test.
  • DETAILED DESCRIPTION
  • Detailed description is given below. Note that in the following description, the unit of content of each element indicating the compositions of the hot-dip coating layer and the molten bath is “mass %”, and the unit will be simply indicated as “%” below unless otherwise specified.
  • First, the method of improving corrosion resistance after coating of hot-dip Al—Zn alloy coated steel sheets, which is most important in the present disclosure, will be described. The presently disclosed hot-dip Al—Zn alloy coated steel sheet contains Al and 0.1% to 3% of Ce in the hot-dip coating layer. Containing Ce in the hot-dip coating layer can improve corrosion resistance after coating, which is the problem of the present disclosure.
  • For a conventional hot-dip Al—Zn alloy coated steel sheet containing no Ce in the hot-dip coating layer, a dense and stable oxide film of Al2O3 is immediately formed around the α-Al phase once the hot-dip coating layer is exposed to the air. Because of the protection function provided by the oxide film, the solubility of the α-Al phase is significantly lower than the solubility of the Zn rich phase. As a result, for a film coated steel sheet using the conventional Al—Zn alloy coated steel sheet as the base steel, if the coating film is damaged, selective corrosion of the Zn rich phase occurs in the interface between the coating film and the hot-dip coating with the damaged part acting as the origin, and the corrosion progresses deep into the sound part of the coating film and causes a large coating film blister. This deteriorates corrosion resistance after coating.
  • On the other hand, for a film coated steel sheet using a hot-dip Al—Zn alloy coated steel sheet which contains a specific amount of Ce in the hot-dip coating layer as the base steel, Ce compounds such as Ce—Si based compounds precipitated in the Zn rich phase are eluted along with the Zn rich phase at the early stage of corrosion, and Ce is incorporated into corrosion products. The Ce-containing corrosion products are very stable, and the corrosion is suppressed at the early stage. In this way, it is possible to effectively suppress the large coating film blister caused by the selective corrosion of the Zn rich phase, which is a problem in the case of a film coated steel sheet using the conventional Al—Zn alloy coated steel sheet as the base steel. As a result, the hot-dip Al—Zn alloy coated steel sheet containing Ce in the hot-dip coating layer shows excellent corrosion resistance after coating.
  • Next, the composition of the hot-dip coating layer of the presently disclosed hot-dip Al—Zn alloy coated steel sheet will be described.
  • When the Ce content in the hot-dip coating layer is less than 0.1%, the amount of eluted Ce during the corrosion is too small to cause the formation of the aforementioned stable corrosion products, so that corrosion resistance after coating cannot be improved. Therefore, the Ce content in the hot-dip coating layer is 0.1% or more. The Ce content is preferably 0.5% or more from the perspective of further improving corrosion resistance after coating.
  • On the other hand, when the Ce content in the hot-dip coating layer exceeds 3%, not only is the effect saturated, but also the corrosion of the Ce compounds occurs severely and the solubility of the entire hot-dip coating layer increases excessively. As a result, the dissolution rate is high even if the corrosion products are stabilized, and this leads to a large blister width and deterioration in corrosion resistance after coating. Therefore, the Ce content in the hot-dip coating layer is 3% or less. The Ce content is preferably 2% or less from the perspective of further improving corrosion resistance after coating.
  • The presently disclosed hot-dip Al—Zn alloy coated steel sheet is a hot-dip Al—Zn alloy coated steel sheet containing 25% to 80% of Al in the hot-dip coating layer. The Al content in the hot-dip coating layer is preferably 45% or more and more preferably 50% or more from the perspective of balancing corrosion resistance with actual operation requirements. The Al content in the hot-dip coating layer is preferably 70% or less and more preferably 60% or less from the same perspective of balancing corrosion resistance with actual operation requirements.
  • When the Al content in the hot-dip coating layer is 25% or more, the aforementioned dendrite solidification of Al occurs in the upper layer existing on the alloy layer existing in the interface with the base steel sheet. As a result, the upper layer is mainly composed of a part where Zn is contained in a supersaturated state and Al is solidified by dendrite solidification, and a remaining interdendritic part, and has a structure with excellent corrosion resistance where the dendrite solidification part is laminated in the thickness direction of the hot-dip coating layer. The Al content is preferably 45% or more in order to stably obtain such a hot-dip coating phase structure.
  • On the other hand, when the Al content exceeds 80%, the content of Zn, which has a sacrificial protection effect against Fe, decreases. As a result, corrosion resistance deteriorates if the base steel sheet is exposed. Generally, the smaller the coating weight is, the easier the base steel sheet is exposed. Therefore, the Al content is preferably 70% or less in order to obtain sufficient corrosion resistance even with a small coating weight. Furthermore, during the hot-dip coating of Al—Zn alloy, the molten bath temperature (hereinafter referred to as “bath temperature”) rises as the Al content increases, and this may lead to actual operation problems. However, the bath temperature would be appropriate and no problem would be caused with the aforementioned Al content.
  • The base steel sheet used for the presently disclosed hot-dip Al—Zn alloy coated steel sheet is not limited to a particular type. For example, a hot rolled steel sheet or steel strip which has been subjected to acid pickling descaling, or a cold rolled steel sheet or steel strip obtained by cold rolling the hot rolled steel sheet or steel strip, may be used.
  • The presently disclosed hot-dip coated steel sheet contains Zn as the balance in the hot-dip coating layer. The content of Zn is not particularly limited and can be appropriately changed according to the contents of other components. However, it is preferably 10% or more. When the Zn content is 10% or more, the hot-dip coating provides a sufficient sacrificial protection effect against Fe, so that better corrosion resistance can be obtained when the steel base is exposed.
  • The presently disclosed hot-dip coated steel sheet preferably contains 0.1% to 10% of Si in the hot-dip coating layer. Si is added in the molten bath to inhibit the growth of the interfacial alloy phase formed in the interface with the base steel sheet and to improve corrosion resistance and workability. Therefore, Si is contained in the hot-dip coating layer. Specifically, in a case where a hot-dip Al—Zn alloy coated steel sheet is subjected to hot-dip coating treatment with a Si-containing molten bath, an alloying reaction between Fe in the steel sheet surface and Al or Si in the bath takes place as soon as the steel sheet is immersed in the molten bath, to form Fe—Al based and/or Fe—Al—Si based compounds. The formation of Fe—Al—Si based compound inhibits the growth of the interfacial alloy phase. By setting the Si content in the molten bath to 0.1% or more, it is possible to inhibit the growth of the interfacial alloy phase. The Si content is more preferably 1.0% or more in order to sufficiently obtain the growth inhibiting effect. On the other hand, when the Si content in the molten bath is 10% or less, it is difficult for Si to precipitate as a Si phase which provides propagating paths for cracks in the produced hot-dip coating layer and deteriorates workability. Therefore, the Si content in the molten bath is preferably 10% or less. Thus, the preferable range of the Si content in the molten bath is 0.1% to 10%. The composition of the hot-dip coating layer of the produced Al—Zn alloy coated steel sheet is substantially the same as the composition of the molten bath. Therefore, the range of the Si content in the hot-dip coating layer is preferably the same as the preferable range of the Si content in the molten bath i.e. a range of 0.1% to 10%.
  • Furthermore, the hot-dip coating layer preferably contains at least one element selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr, and B in a total amount of 0.01% to 10%. This is because these elements provide an effect of improving the stability of corrosion products and delaying the progressing of corrosion.
  • The chemical composition of the hot-dip coating layer can be verified by, for example, immersing and dissolving the hot-dip coating layer in, for example, hydrochloric acid, and performing ICP emission spectral analysis or atomic absorption analysis on the solution. This method is intended to be an example rather than a limitation. Any method may be used as long as it can precisely quantify the chemical composition of the hot-dip coating layer.
  • The components other than the aforementioned chemical composition of the hot-dip coating layer are inevitable impurities. This means that it is within the scope of the present disclosure to include inevitable impurities and other trace element unless existence thereof adversely affects the operation and effect of the present disclosure.
  • The hot-dip coating layer contains no Mg. In this way, it is possible to inhibit the occurrence of dross resulting from the oxidation of Mg, which is an oxidizable element, thereby inhibiting the occurrence of surface defects caused by the dross.
  • Next, the method of producing the presently disclosed hot-dip Al—Zn alloy coated steel sheet will be described.
  • The presently disclosed hot-dip Al—Zn alloy coated steel sheet can be produced by, for example, galvanizing facilities such as a continuous galvanizing line, and conventional methods may be used except for the composition management of the molten bath.
  • The composition of the molten bath includes 25 mass % to 80 mass % of Al and 0.1% to 3% of Ce, with the balance being Zn and inevitable impurities. By applying a molten bath of such a composition, it is possible to produce the presently disclosed hot-dip Al—Zn alloy coated steel sheet with the aforementioned hot-dip coating layer structure. As previously mentioned, it is preferable to contain 10% or more of Zn in the molten bath in order to provide the hot-dip coating layer with a sufficient sacrificial protection effect against Fe, and to contain 0.1% to 10% of Si in the molten bath in order to inhibit the growth of the interfacial alloy layer.
  • It is possible to add any element other than the aforementioned Al, Zn, Si and Ce in the molten bath as long as the effect of the present disclosure is not impaired. In particular, it is preferable to contain at least one element selected from Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10% in the molten bath, to improve the corrosion resistance of the produced hot-dip Al—Zn alloy coated steel sheet as previously mentioned.
  • In this way, it is possible to obtain the presently disclosed hot-dip Al—Zn alloy coated steel sheet with excellent corrosion resistance after coating.
  • EXAMPLES
  • (Samples 1 to 13)
  • Each sample hot-dip Al—Zn alloy coated steel sheet was produced by a continuous galvanizing line (CGL) using a cold rolled steel sheet with a sheet thickness of 0.8 mm produced by a conventional method as the base steel sheet, where the bath temperature of the molten bath was as listed in Table 1, and the coating weight was 50 g/m2 per side and 100 g/m2 for both sides.
  • (1) Composition of Hot-Dip Coating Layer
  • Each sample hot-dip Al—Zn alloy coated steel sheet was punched out to 100 mm in diameter, and immersed in hydrochloric acid to dissolve the hot-dip coating layer. Subsequently, the composition of the dissolving solution was verified by performing quantification based on ICP emission spectral analysis. The composition of the hot-dip coating layer of each sample is listed in Table 1.
  • (2) Evaluation of Corrosion Resistance after Coating
  • Each sample hot-dip Al—Zn alloy coated steel sheet was sheared into a size of 90 mm×70 mm, and then subjected to zinc phosphate treatment as chemical conversion treatment, followed by electrodeposition coating, intercoating and top coating, which was similar to the coating treatment for automobile outer panels. The zinc phosphate treatment, electrodeposition coating, intercoating and top coating here were performed under the following conditions.
  • [Zinc Phosphate Treatment]
  • Chemical conversion treatment was performed using a degreasing agent: FC-E2001, a surface adjusting agent: PL-X, and a chemical conversion treatment agent: PB-AX35M (temperature: 35° C.) manufactured by Nihon Parkerizing Co., Ltd., where the free fluorine concentration of the chemical conversion treatment liquid was 200 mass ppm, and the immersion time of the chemical conversion treatment liquid was 120 seconds.
  • [Electrodeposition Coating]
  • Electrodeposition coating was performed using an electrodeposition coating material: GT-100 manufactured by Kansai Paint Co., Ltd., to obtain a coating thickness of 15 μm.
  • [Intercoating]
  • Spray coating was performed using an intercoating material: TP-65-P manufactured by Kansai Paint Co., Ltd., to obtain a coating thickness of 30 μm.
  • [Top Coating]
  • Spray coating was performed using a top coating material: Neo6000 manufactured by Kansai Paint Co., Ltd., to obtain a coating thickness of 30 μm.
  • Subsequently, samples for evaluating corrosion resistance after coating were prepared by sealing 5 mm of the end of the surface to be evaluated and the surface not to be evaluated (back surface) with a tape, and then making a cross cut in the center of the surface to be evaluated with a depth reaching the base steel of the hot-dip coated steel sheet, a length of 60 mm and a central angle of 90° by a utility knife, as illustrated in FIG. 1.
  • A corrosion acceleration test was performed using the samples for evaluation along the cycle illustrated in FIG. 2. The corrosion acceleration test started from humid atmosphere and was conducted for 60 cycles. Subsequently, the width of the coating film blister which was the largest coating film blister from the damaged part (maximum coating film blister width) was measured, and the corrosion resistance after coating was evaluated based on the following criteria. The evaluation results are listed in Table 1.
  • Good: Maximum Coating Film Blister Width≤1.5 mm
  • Fair: 1.5 mm<Maximum Coating Film Blister Width 2.0 mm
  • Poor: 2.0 mm<Maximum Coating Film Blister Width
  • TABLE 1
    Corrosion Bath
    Composition of Hot-Dip Resistance Temper-
    Coating Layer/mass % after ature
    No. Al Zn Si Ce Coating ° C. Remarks
    1 55 Balance 1.6 Poor 600 Comparative
    Example
    2 55 Balance 1.6  0.03 Poor 600 Comparative
    Example
    3 55 Balance 1.6 0.2 Good 600 Example
    4 55 Balance 1.6 1.0 Good 600 Example
    5 55 Balance 1.6 2.0 Good 600 Example
    6 55 Balance 1.6 3.5 Fair 600 Comparative
    Example
    7 55 Balance 1.6 5.0 Poor 600 Comparative
    Example
    8 25 Balance 0.5 2.0 Good 520 Example
    9 35 Balance 1.0 2.0 Good 580 Example
    10 70 Balance 1.6 2.0 Good 660 Example
    11 80 Balance 3.0 2.0 Good 690 Example
    12 80 Balance 6.0 2.0 Good 690 Example
    13 80 Balance 10.0 2.0 Good 690 Example
  • According to Table 1, the samples of the present disclosure were different from the samples of the comparative examples and had a maximum coating film blister width of 1.5 mm or less. Therefore, it is understood that hot-dip Al—Zn alloy coated steel sheets with excellent corrosion resistance after coating were obtained. Furthermore, it is understood from the samples of the present disclosure that, by limiting the Ce content in the hot-dip coating layer of each sample within an appropriate range, hot-dip Al—Zn alloy coated steel sheets with excellent corrosion resistance after coating can be obtained.
  • INDUSTRIAL APPLICABILITY
  • The presently disclosed hot-dip Al—Zn alloy coated steel sheet has excellent corrosion resistance after coating, and can be applied in a wide range of fields such as automobiles, household electric appliances, and building materials. Particularly in the field of automobiles, when the present disclosure is applied to a high strength steel sheet, it can be used as a surface-treated steel sheet which achieves automobile weight reduction and high corrosion resistance.

Claims (16)

1. A hot-dip Al—Zn alloy coated steel sheet comprising a base steel sheet and a hot-dip coating layer formed on a surface of the base steel sheet, wherein the hot-dip coating layer contains, by mass %, Al: 25% to 80% and Ce: 0.1% to 3%, the balance being Zn and inevitable impurities.
2. The hot-dip Al—Zn alloy coated steel sheet according to claim 1, wherein the hot-dip coating layer further contains Si: 0.1 mass % to 10 mass %.
3. The hot-dip Al—Zn alloy coated steel sheet according to claim 1, wherein the Al content in the hot-dip coating layer is 45 mass % to 70 mass %.
4. The hot-dip Al—Zn alloy coated steel sheet according to claim 1, wherein the Ce content in the hot-dip coating layer is 0.5 mass % to 3 mass %.
5. The hot-dip Al—Zn alloy coated steel sheet according to claim 1, wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
6. The hot-dip Al—Zn alloy coated steel sheet according to claim 2, wherein the Al content in the hot-dip coating layer is 45 mass % to 70 mass %.
7. The hot-dip Al—Zn alloy coated steel sheet according to claim 2, wherein the Ce content in the hot-dip coating layer is 0.5 mass % to 3 mass %.
8. The hot-dip Al—Zn alloy coated steel sheet according to claim 3, wherein the Ce content in the hot-dip coating layer is 0.5 mass % to 3 mass %.
9. The hot-dip Al—Zn alloy coated steel sheet according to claim 6, wherein the Ce content in the hot-dip coating layer is 0.5 mass % to 3 mass %.
10. The hot-dip Al—Zn alloy coated steel sheet according to claim 2, wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
11. The hot-dip Al—Zn alloy coated steel sheet according to claim 3, wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
12. The hot-dip Al—Zn alloy coated steel sheet according to claim 4, wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
13. The hot-dip Al—Zn alloy coated steel sheet according to claim 6, wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
14. The hot-dip Al—Zn alloy coated steel sheet according to claim 7, wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
15. The hot-dip Al—Zn alloy coated steel sheet according to claim 8, wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
16. The hot-dip Al—Zn alloy coated steel sheet according to claim 9, wherein the hot-dip coating layer contains at least one selected from the group consisting of Mn, V, Cr, Mo, Ti, Ni, Co, Sb, Zr and B in a total amount of 0.01% to 10%.
US16/330,158 2016-09-05 2017-08-24 HOT-DIP Al-Zn ALLOY COATED STEEL SHEET Abandoned US20190185970A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016172945 2016-09-05
JP2016-172945 2016-09-05
PCT/JP2017/030323 WO2018043286A1 (en) 2016-09-05 2017-08-24 Al-Zn-BASED HOT-DIP PLATED STEEL SHEET

Publications (1)

Publication Number Publication Date
US20190185970A1 true US20190185970A1 (en) 2019-06-20

Family

ID=61305351

Family Applications (1)

Application Number Title Priority Date Filing Date
US16/330,158 Abandoned US20190185970A1 (en) 2016-09-05 2017-08-24 HOT-DIP Al-Zn ALLOY COATED STEEL SHEET

Country Status (8)

Country Link
US (1) US20190185970A1 (en)
EP (1) EP3508610B1 (en)
JP (1) JP6315153B1 (en)
KR (3) KR20220013591A (en)
CN (1) CN109689916B (en)
MX (1) MX2019002535A (en)
TW (1) TWI639726B (en)
WO (1) WO2018043286A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102153172B1 (en) * 2018-08-30 2020-09-07 주식회사 포스코 Aluminium-Zinc alloy plated steel sheet having excellent hot workabilities and corrosion resistance, and method for the same
CN110923603A (en) * 2019-12-09 2020-03-27 晋江安能建材制造有限公司 High-heat-resistance hot-dip aluminum-zinc plated steel plate and production method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4722871A (en) * 1986-08-14 1988-02-02 Cosmos Engineering, Inc. Zinc-aluminum alloy coatings for steel
CN101314828A (en) * 2008-07-01 2008-12-03 葫芦岛锌业股份有限公司 Quaternary alloy for dip coating and producing method thereof
US20100119869A1 (en) * 2008-11-13 2010-05-13 Changshu Huaye Steel Strip Co., Ltd Hot-dipped zn-al-si-mg-re steel plate
CN101880800A (en) * 2010-05-26 2010-11-10 上海大学 High Al system Al-Zn-Si-Ti hot dip plating alloy with small crystal particles and high corrosion resistance
US20160002753A1 (en) * 2013-02-28 2016-01-07 Nippon Steel & Sumikin Coated Sheet Corporation Aluminum-zinc plated steel sheet and method for producing the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4102035B2 (en) * 2000-04-18 2008-06-18 新日本製鐵株式会社 Plating product with excellent corrosion resistance and manufacturing method thereof
JP2002012959A (en) 2000-04-26 2002-01-15 Nippon Steel Corp Steel sheet plated with al based metal with corrosion resistance in plated part and end face
CN101405421B (en) 2006-03-20 2012-04-04 新日本制铁株式会社 Highly corrosion-resistant hot dip galvanized steel stock
CN101545069A (en) * 2009-02-13 2009-09-30 常熟华冶薄板有限公司 Hot-dipping zinc, aluminum, silicon and magnesium rear-earth steel plate
CN101457320A (en) * 2009-01-04 2009-06-17 上海大学 Al-Zn-Mg-Si alloy for hot dipping steel
AU2011216352B2 (en) * 2010-02-18 2013-06-20 Nippon Steel Coated Sheet Corporation Hot-dipped steel and method for producing same
TWI482880B (en) * 2012-02-28 2015-05-01 Nippon Steel & Sumikin Coated Coated steel sheet complising aluminium-zinc base alloy plating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4722871A (en) * 1986-08-14 1988-02-02 Cosmos Engineering, Inc. Zinc-aluminum alloy coatings for steel
CN101314828A (en) * 2008-07-01 2008-12-03 葫芦岛锌业股份有限公司 Quaternary alloy for dip coating and producing method thereof
US20100119869A1 (en) * 2008-11-13 2010-05-13 Changshu Huaye Steel Strip Co., Ltd Hot-dipped zn-al-si-mg-re steel plate
CN101880800A (en) * 2010-05-26 2010-11-10 上海大学 High Al system Al-Zn-Si-Ti hot dip plating alloy with small crystal particles and high corrosion resistance
US20160002753A1 (en) * 2013-02-28 2016-01-07 Nippon Steel & Sumikin Coated Sheet Corporation Aluminum-zinc plated steel sheet and method for producing the same

Also Published As

Publication number Publication date
KR20190045297A (en) 2019-05-02
JP6315153B1 (en) 2018-04-25
TW201812054A (en) 2018-04-01
CN109689916B (en) 2023-08-01
EP3508610A1 (en) 2019-07-10
MX2019002535A (en) 2019-07-01
KR20210068627A (en) 2021-06-09
CN109689916A (en) 2019-04-26
EP3508610B1 (en) 2022-06-22
JPWO2018043286A1 (en) 2018-09-13
EP3508610A4 (en) 2019-07-10
TWI639726B (en) 2018-11-01
KR20220013591A (en) 2022-02-04
WO2018043286A1 (en) 2018-03-08

Similar Documents

Publication Publication Date Title
EP3266900B1 (en) Molten al-zn-mg-si-plated steel sheet
CN113557318B (en) Coated steel sheet
AU2014240655B2 (en) Hot-dip Al-Zn alloy coated steel sheet and method for producing same
JP6112131B2 (en) Molten Al-Zn-based plated steel sheet and method for producing the same
CN110352261B (en) Hot-dip Al-based steel sheet and method for producing same
WO2019130534A1 (en) MOLTEN Zn-BASED PLATED STEEL SHEET HAVING SUPERIOR CORROSION RESISTANCE AFTER BEING COATED
JP6065043B2 (en) Molten Al-Zn-based plated steel sheet and method for producing the same
WO2018181391A1 (en) Hot-dipped al coated steel sheet and method for producing hot-dipped al coated steel sheet
JP3684135B2 (en) Si-containing high-strength hot-dip galvanized steel sheet with excellent corrosion resistance and method for producing the same
WO2020213687A1 (en) Plated steel sheet
EP3508610B1 (en) Hot-dip al-zn alloy coated steel sheet
JP2016060945A (en) MOLTEN Al-BASED PLATED SHEET STEEL
JP2002173753A (en) HOT DIP Zn-Al ALLOY PLATED STEEL SHEET HAVING EXCELLENT BLACKENING RESISTANCE AND ITS PRODUCTION METHOD
JP6065042B2 (en) Molten Al-Zn-based plated steel sheet and method for producing the same
JP2016060946A (en) MOLTEN Al-BASED PLATED SHEET STEEL
JP6337711B2 (en) Fused Al-based plated steel sheet
JP7120166B2 (en) Method for producing hot-dip Al-Zn-based plated steel sheet
JP5604784B2 (en) Method for producing alloyed hot-dip galvanized steel sheet with good plating properties

Legal Events

Date Code Title Description
AS Assignment

Owner name: JFE STEEL CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YOSHIDA, MASAHIRO;MATSUZAKI, AKIRA;REEL/FRAME:048491/0718

Effective date: 20190116

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION